Azo dyestuffs



Patented Sept. 27, 1932 Q UN TED JOSEF HILGEB AND mnnwrnnnmnnn, or,coLoaim-MoLHEIM-oN-THE EINE, enn- I MANY, ASSIGNORS 'ro GENERAL ANILINE wonxs mc; or new iron-K, n. Y., A

V CORPORATION 01* ELAW RE No Drawing. Application filed March 2o, 19ao,'ser1a1 No. 437,595, slit i Germany March so, 1929.,

The present invention relates to new azo dyestufi's containing copper, more particularly it relates to dyestuffs which may :be represented by the probable general formula wherein R stands for an aromaticnucleus, for instance, of the benzeneseries or for a benzoyl group and wstands'for a group inducing solubility-in water such as -COOH, SO I-I, -OCH .COOH, the group NH.R.w standing, in 2-01.v 3' position of the naphthalene nucleus and wherein all nuclei may be further substituted, for instance, by COOH, SO H, -OH, halogen, alkyl and alkoxg.

Our new dyestu s are obtainable by coupling in alkaline solution a tetrazotized benzidine ortho ortho' dicarboxylic acid compound with two molecules of the same or different 2 or 3-phenol or benzoylamino' 5-naphthol-7-sulfonic acid compounds in which the ph'enyl orbenzoyl residue is at least once substituted by a group inducing solubility in water, in the presence of an agent yielding copper such as copper sulfate, copper hydroxide, tetrammi ne cupric sulfate or finely divided metallic copper. Our new copper compounds are also obtainable by treating the dyestuffs in substance with an ing processby adding a suitable copper compound or finely divided copper to an ordinary agent yielding copper. 7 The new dyestuffs" I are furthermore obtainableduring the dye metallic lustrous owders solublerin water, dyeing vegetable bers violet-to blue shades of excellent fastness-to light and ironing.

The following examples serve to illustrate our invention, without limiting it thereto Y Example 1.--1072 .parts by weight ofthe azo dyestulf obtainable from 1 molecular proj portion of tetrazotized 4.4-diamino-diphenyl-3.3-dicarboxylic acid and two molecular proportions of 7'-sulfo-5-hydroxy- 2- naphthyl 4 aminophenoxy acetic 7 acid (prepared by the interaction of 2.5-dihydroxynaphthalene-7-sulfonic acid with 4- amino-phenoxy acetic acid in the presence of g, sodium bisulfite) are dissolved in 20,000 parts.

of Water. The solution is rendered weakly acid with acetic acid, while stirring, and a solution. of 280 parts by Weight of crystallized copper sulfate in 10 times the quantity of water .ispthen added alt-80? 0-. After furtherlieating for 2 hours to 7080 C. the completely precipitated W dyestufl is, filtered and convertedby means of sodiumcarbonate into its sodium salt. Thelatter is saltedout from its aqueous solution by means of sodium chloride, pressed 1 and dried. The dyestuff contining copper is, a dark powder witha metallic luster, readily soluble in water and dyesvegetablefibers violet to blue shades from asodium sulfate-sodium carbonate bath. p following formula I HO3S NHO OOOH l ooonorno V Cu: H .J

Besidesits clearness of shadevtheudyestufi is distinguished by excellent fastness to ironing, to: alkali and to light; Y

Our newazo dyestufis generally are darli- In its free state it has probably the The copper compound of the dyestufi' obtainable from one molecular proportion of 4. 1 diaminodiphenyl-3.3-dicarboxylic acid and two molecular proportions of 7 -sulfo- 5- hydroxy-2- naphthyl-t-aminophenylthioglycolic acid (prepared by the interaction of 2,5 dihydroxynaphthalene 7 4 sulfonic acid with 4-aminophenylthioglycolic acid (pre- Killfid according to the instructions given in onatshefte fiir Chemie, vol. 28, page 278) in the presence of bisulfite): yields somewhat more bluish shades of similar fastness properties. i

By means of copper compounds produced in an analogous manner from dyestuffs obtainable from one molecular proportion of tetrazotiz'ed 4.4-diaminodiphenyl-3.3-dicarboxylic acid and 2 molecular proportions of different 7 sulfo-5- hydroxy-2 naphthylamino-aryl-hydroxy acetic acids or arylthioglycolic acids there are 7 obtained similar shades of similar fastness properties. Thus, for example, reddish-blue shades are obtained on vegetable fibers with a copper compound of the azo dyestufi' produced in any desired manner from one molecular proportion of tetrazotized 4:.4--diaminodiphenyl-' 3.3-dicarboxylic acid, one molecular proportion of 7 -sulfo-5-hydroxy-2-naphthyl-tamino-EZ-methyl (or Q-chloro) -phenoxy acetic acid, prepared by the interaction of 2.5-dihydroxynaphthalene-7-sulfonic 4-amino-2 methyl (or 2 chloro) phenoxy acetic acid in the presence of sodium bisulfite and one molecular proportion of 7 sulfo 5 hydroxy 2 naphthyl 4 amino phenoxy acetic acid.

The analogous dyestuffs containing copper which, instead of the arylhydroxy acetic acid residues contain aryl hydroxy beta-propionic acid residues, likewise yield dyeings of similar shades and fastness properties. 4- (or 3) -aminophenoxy-beta-propionic acid for example is prepared by the interaction of V the sodium salt of 4- (or 3-) nitrophenol with a neutral solution of beta-chloropropionic acid and subsequent reduction with iron and acetic acid. For the introduction of the copper other agents yielding copper, such as, for example, finely divided copper and th like, can be used.

acid with pension a suspension of the tetrazo compound from 27 2' parts by weight of 4.4-diaminodiphenyl 3.?1edicarboxylic acid is run in, while cooling; when thecoupling'is complete the mixture is diluted with hot water and filtered from unchanged eopperhydroxide, which is likewise boiled several times with hot water. The dyestufi' containing copper is separated from the solution by the addition of-sodium chloride. In its free state it has the probable formula.

sagas i Our I r i V In this combination the 2.[4=-sulfophenyl] amino 5 hydroxy-naphthalene 7 sulfonic acid can be replaced among others bytwo similar or dissimilar molecules of other 2- aryl e amino 5 hydroxy naphthalene -,7 -sulfonic acids containing sulfonic acid groups in the aryl residue; it can be replaced, for example by the 7 -sulfo-5-hydroxy-2t-naphthylamino-benzyl-omega-sulfonic acid of the formula noasm-Nn-oomsoan tn i and similar compounds without afiiecting the satisfactory fastness properties and clear shades of the copper compounds. The cop- .-pering can of course also be carried out on the finisheddyestuff'in accordance with the process described in Example 1 or by other known coppering methods.

EE'wampZe 3. When coppering according to the method described in Example 1 the azo dyestufi-which is obtainable by the combination of one molecular proportion of 4.4:- diaminodiphenyl-3.3-dicarboxylic acid and two molecular proportions of 2(3-carboxyphenyl) amino-5-hydroXynaphthalene-7-sul fo nic acid, a copper compound is obtained dyeing vegetable fibers powerful clear red- .dishblue shades of excellent fastness properties. The dyestufi has in its'free state probably the followingpformula Cliz I l NHQ L :11 O OH Similar dyestuffs are obtainable by causing agents yielding copper to act on azo dyestufis obtainable by coupling tetraz'otized L4"-di aminodiphenyl-3.3-dicarboxylic acid with the condensation products obtainable in the customary manner by the bisulfite process from Q-amino-5-hydroxy-naphthalene-7-sulfonic acid or 1.6-dihydroxy-naphthalene-3- sulfonic acid and amino-benzonitriles such as for example 3-amino-benzo-nitrile. The compounds thus obtainable are presumably arylated 2-amino-5-hydroxy-naphthalene-7- sulfonic acids containing carbon-amide-resi dues (CONH in the aryl residue.

Ewample l ;.-A dye bath is made up from I 2% of the azo dyestufi obtainable from one molecularproportion of tetrazotized 4.4f-diaminodiphenyl-3.3 dicarboxylic acid and two molecular proportions of 7-sulfo- 5 -hydroxy-2-naphthyl-S-amino cinnamic 3016.

a1 V 0.2% of copper sulfate, 20% of sodium sulfate and 2% of sodium carbonate. The cotton is entered into-this dye bath at 40-50" (3., the temperature is slowly raised toboiling and maintained for to 1 hour. After rinsing and drying a clear bluish violet dyeing is obtained of excellentfastness to light, ironing and alkali.

The dyestufl' is also very suitable for dyeing halI" woolen articles.

Analogous copper containing dyestufis are obtained when coppering according to the directions given in Examples 1 or 2 dyestufi's prepared from one molecular proportion boxvlic acids and two molecular proportions of 'i-sulfo 5-hydroxy-2-naphthyl-3-amino cinnamic acid. I. v Example 5.-920 parts by weight of the azo dyestuff from one molecular proportion of tetrazotized 4.4-diamino-diphenyl-3L3-di-' carboxylic acid and two molecular proporof 4.4-diamino-diphenyl-3.3'-dicar tions of "2.[2-carboxy-benzoyl] amino- 5-hy droxynaphthale'ne 7 sulfonicacid (obtaim able'bydecomposition.of 2-amino-5-hydroxynaphthalene-7-sulfonic acid with phthalic acid anhydride in an aqueous solution in thepresence of sodium acetate; grey powder easily soluble in water, alkalies and diluted mmoral acids) are dissolved in 20,000 parts by weight of water with the addition of some sodium carbonate. The'solution'is then acidified with.

acetic acid while stirringand a solution of 300 parts by weight ofcrystallized-cop'per sulfate in 5 times the quantityfof water is then added. After heating ,for two hours at 70-80 O. the completely precipitated dye stuff is filtered and converted bymeans of sodium carbonate into its sodium salt.- It

dyes vegetable fibers from the sodium sulfate; 0 sodium carbonate bath violet'shades of excels lent fastness properties. In its free state the A dyestufi has the following formula Ewample 6.VVhen the coppering process tionof the tetrazotized 4.4'-diamino-diphenyl-8.3- dicarboxylic acid with two molecular proportions of 7 sulfo-5-hydroxy-2'-naph- I ,thyl A aminophenyl acetic acid, a copper compound is obtained which dyes vegetable fibers violet blue shades.

portions of 7- sulfo-5-hydroxy-2-naphthyld-amindhydro-cinnamic acid (prepared by the interaction of 2-.5-dihydroxynaphthalene- The copper com-. pound obtainable in the same manner from.

7-sulfonic acid with4-amino-hydro-cinnamic acid in the presence of sodium bisulfite) yields similar, equally fast shades. 7

Such copper compounds can obviously also be obtained by the processes described in Examples 2 or 3 or by other coppering processes. I

Example 7.-1072 parts by weight of the azo dyestufi obtainable from one molecular proportion of tetraz otized 4:.l-diaminodiphenyl-3.3'-dicarboxylic acid, one molecular proportion of 7-sulfo-5.-hydroxy-2'-naphthyl-- o i-amlnophenoxy aceticacldand one molecu lar proportion of 6-sulfo-8' -hydroXy-2"- naphthyll-aminophenoxy acetic acid are dissolved in 20,000 parts of water. The 'solution is acidified with acetic acid and a solu-' tion of 300 parts by weight of copper sulfate in 5 times the quantity of water isadded at 7080 C. After heating for 2 hours the completely precipitated dyestufl' is filtered and converted by means of sodium carbonate into its sodium salt. a It dyes vegetable fibers brownish-violet shades. The dyestufi has in its free state the following formula Example 8.1270 parts by weight of the azo dyestuff obtained from one molecular proportion of 4.4'-diamino-diphenyl-3.3-dicarboxylic acid and two molecular proportions of 7-sulfo-5-hydroXy-2-naphthyl-2-amino-1.1-diphenyl etherl-sulfonic acid of the formula v 00011 S O:1H

OOOH

SOQH

{prepared by the interaction of 2.5-dihy- .droxynaphthalene 7 sulfonic acid with 2- amino-1.1-diphenylether-l-sulfonic acid in the presence ofsodium bisulfite) are dissolved in 20,000 parts of water. The solution is acidifiedwith acetic acid and asolution of 300 parts by Weight of "crystallized-copper sulfate is added, while stirring. After heating for two hours at 7 080 G. the completely precipitated dyestufi is filtered and convert- I ed into its sodium salt. The latter is a powder readily soluble in water with a violet coloration and dyes vegetable fibers from the sodium sulfate-sodium carbonate bath bluish- Violet shades of excellent fastncss to ironing and light.

Example 9. vVhen the copperingprocess of Example 1 is applied to an azo dyestuff obtainable by coupling one molecular proportion of tetrazotized 4.4-diaminodiphenyl-3.3-dicarboxylic acid with two molecular proportions of 7-sulfo-5-hydroxy-2- naphthyl 4 aminophenol glycerol ether, there is obtained a dyestuflf which dyes vegetable fibers reddish blue shades. The dyestuif has in its free state the following formula 4111000112. o'HorLcmoH Ouz Similar dyestuifsare obtained by using instead of the 7-sulf0-5-hydroXy-2-naphthyl-4-aminophenylglycerol ether the 7 sulfo -i-hydroxy- 2-naphthyl-4 -aminophenol glycolic'ether or the 7 ,-sulfo-5'-hydroxy- 2-naphthyl-4-aminophenol glycolic ether sulfuric acid ester. H V

We claim I 1. As new products, copper-containing azo dyestufi s'of the probable general formula wherein NHltai stands in 2 or 3 position of the naphthalene nucleus, R means ajrad'ical of the benzene seriesora benzoyl radical and trous substances, easily soluble inwater and dyeing vegetable fibers violet to blue shades of excellent fastness to light and ironing.

' 3. 'As new products, copper-containing azo dyestuffs of the probable general formula;

00 stands for a group inducing solubility inv bility in water and wherein all nuclei may be substituted by alkyl and halogen, being generally dark metallic lustrous substances, easily, soluble in water and dyeingvegetable fibres water, being generally dark metallic lusviolettoblue shades of excellent fastness to trous substances, easily soluble in Water and light and ironing. I dyeing vegetable fibers violet to blue shades 4. As new products, copper-containing azo of excellent fastness to light and ironing. dyestuffs of the probable general formula i i a V oooH ooon I INK-G v i 7 0H 3 i ooon y coon V 1 4g N=N J i I 011] 2. As new products, copper-containing azo dyestufi's of the probable general formula wherein :0 stands for a group inducing solubility in water and wherein all nuclei may be further substituted by COOH, S0 H, OH, alkyl or alkoxy groups, or halogen atoms, being generally dark metallic luswherein all nuclei may be further substituted by'.COQH, -SO H, OH, alkyl or alkoxy groups, or halogen atoms, being genera'lly'dark metallic-lustrous substances, easily soluble in water and dyeing vegetable fibers violet to blue shades of excellent fastness to light and ironing.

wherein 4 stands for a group induclng solud 5. As new products, copper-containing azo 8. As a new product, the copper-containing dyestuffs of the probable general formula: azo dyestufl of the following formula:

wherein all nuclei may be substituted by alkyl and halogen, being generally dark metallic lustroussubstances, easily' soluble in water and dyeing vegetable fibers violet to blue shades of excellent fastness to light and iron ing.

6. As a new product, the copper-containing azo dyestufi of the probable general formula V coon HOaS 41110 N=N V ooori (5H coon OOOH HOaS NH@ N=N a i Q H03 NHQ NZN OOH being a dark metallic lustrous powder, easily soluble in water and dyeing ve'getablefibres violet shades of excellent fastness to ironing, alkali and light.

- In testimony whereof, .we aflix our signatures. I

' J OSEF HILGER.

KARL WIEDEMANN.

being a dark metallic lustrous powder, easily soluble in water and dyeing vegetable fibers powerful clear reddish shades of excellent fastn ess to light and ironing.

7 As a new product the copper-containing a-zo dyestufi of the following formula:

being a dark metallic lustrous powder, easily soluble in water and dyeing vegetable fibres violet to blue shades of excellent fastness to ironing, alkali and light. 

